The goal of the current study is to better understand the role of storm dynamics on stream water chemical variability in a highly polluted urban-fringe watershed. The study was conducted in the upper reach of the Arroyo Seco watershed located on the eastern edge of the densely urbanized Los Angeles basin in California. During the 2008-2009 study period, high-frequency stream water observations of chloride, fluoride, sulfate, and nitrate were monitored through a series of storm events and were compared to pre- and post-winter storm season geochemical soil profiles. Of the four solutes measured, nitrate demonstrated hydrologically enhanced behavior. Chloride, fluoride, and sulfate exhibited enhanced behavior initially (first flush), but transitioned to dilution behavior as the season progressed. Soil chemistry analyses in the riparian zone confirmed the abundance of nitrate on the soil surface, serving as a source for stream water nitrate. Observations and analyses collectively suggest that the chemical variability observed during the storms is dependent not only on discharge, but also on the magnitude and intensity of rainfall, the length of the antecedent dry period, and riparian soil composition. A further understanding of these factors will ultimately improve geochemical models for prediction of downstream chemical loads from regional urban-fringe watersheds. © 2013 Springer-Verlag Berlin Heidelberg.